Herein, the straightforward C-3 functionalization of 4-dimethylaminopyridine (DMAP) backbone is disclosed. An efficient halogen-metal exchange procedure from 3-bromo DMAP 1 is reported providing a large panel of C-3 functionalized DMAPs. In addition, a Pd- catalysed C–N cross-coupling reaction is also described furnishing new 3-amino DMAPs. These new functionalization pathways led to the resolution-free synthesis of three new ...